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DOI: 10.1055/s-2006-939078
A New Domino Process Initiated by Acetylide Addition onto trans-1,2-Dibenzoyl-3,5-cyclohexadienes: Observation of Sequential C-C, C-O Bond Formation/Cleavage Reactions
Publication History
Publication Date:
05 May 2006 (online)
Abstract
Domino acetylide addition/rearrangement reactions on trans-1,2-dibenzoyl-3,5-cyclohexadienes with lithium acetylides furnish stereodefined 3-ylidene-2,3-dihydrofurans and polysubstituted benzophenones; the overall domino process entails three bond formations (two C-C and one C-O) and two bond cleavages (one C-C and one C-O) in a single operation.
Key words
domino reaction - zirconacycle - acetylide addition - 3-ylidene-2,3-dihydrofurans - benzophenones
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References and Notes
CCDC 294449 contains the crystallographic data for 3d. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
8CCDC 294450 contains the crystallographic data for 4f. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
9
Typical Procedure for the Cycloaddition Reaction of Zirconacyclopentadienes with trans
-1,4-Diphenylbut-2-ene-1,4-dione.
To a solution of Cp2ZrCl2 (0.32 g, 1.1 mmol) in THF (5 mL) was added n-BuLi (1.6 M THF solution, 2.2 mmol) at
-78 °C. After stirring for 1 h at the same temperature, 3-hexyne (0.16 g, 2 mmol) was added and the reaction mixture was warmed up to r.t. and stirred for 1 h. Then, BiCl3 (0.38 g, 1.2 mmol), which was dried using a heat gun at ca. 500 °C for 30 min under vacuum, and 1,4-diphenyl-but-2-ene-1,4-dione (0.47 g, 2.0 mmol) were added and the mixture was stirred at 50 °C for 12 h. The reaction mixture was quenched with 3 N HCl and extracted with EtOAc. The extract was washed with H2O, brine and dried over MgSO4. The solvent was evaporated in vacuo and the residue was purified by chromatography on silica gel (PE-EtOAc, 20:1). A light-yellow solid of 3a (265 mg, 66%) was obtained.
trans-(6-Benzoyl-2,3,4,5-tetraethylcyclohexa-2,4-dienyl)phenylmethanone(3a): 1H NMR (Me4Si, CDCl3): δ = 0.77 (t, J = 7.5 Hz, 6 H), 0.98 (t, J = 7.5 Hz, 6 H), 1.66-1.78 (m, 2 H), 2.10-2.46 (m, 6 H), 4.08 (s, 2 H), 7.41-7.52 (m, 4 H), 7.52-7.57 (m, 2 H), 7.77-7.81 (m, 4 H). 13C NMR (Me4Si, CDCl3): δ = 13.0, 14.7, 20.7, 25.8, 49.2, 127.5, 128.0, 128.4, 132.2, 137.2, 137.7, 199.7. HRMS (MALDI/DHB): m/z calcd for C28H33O2 [M + H]+: 401.2481; found: 401.2475.
Typical Procedure for the Domino Reactions of trans
-1,2-Dibenzoyl-3,5-cyclohexadiene Products 3 with Lithium Acetylides.
To a solution of 1-hexyne (0.12 mL, 1.0 mmol) in THF (5 mL) was added n-BuLi (0.63 mL, 1.6 M in hexane) at
-78 °C. After the mixture was stirred at the same temperature for 1 h, the mixture was warmed up to 0 °C and stirred for 30 min. Then, (6-benzoyl-2,3,4,5-tetraethyl-cyclohexa-2,4-dienyl) phenylmethanone 3a (0.20 g, 0.5 mmol) was added; the resulting reaction mixture was warmed up to r.t. and stirred for 24 h. The mixture was quenched with an aq solution of NH4Cl and extracted with EtOAc. The extract was washed with H2O, brine and dried over MgSO4. The solvent was evaporated in vacuo and the residue was purified by chromatography on silica gel by first using a mixed solvent of PE-CH2Cl2 (25:1) as an eluent to give 4a (120 mg, 52%) as a white solid. Compound 5a (60 mg, 41%) was obtained as a yellow liquid by using a second eluent (PE-CH2Cl2, 1:1).
(E)-3-Butylidene-2,5-diphenyl-2-(2,3,4,5-tetraethyl-phenyl)-2,3-dihydrofuran (4a): column chromatography on silica gel (PE-CH2Cl2, 25:1) afforded 120 mg (52%) product as a white solid. 1H NMR (Me4Si, CDCl3): δ = 0.92 (t, J = 7.4 Hz, 3 H), 1.03 (t, J = 7.1 Hz, 3 H), 1.09-1.26 (m, 9 H), 1.47 (q, J = 7.5 Hz, 2 H), 2.12-2.28 (m, 2 H), 2.54-2.73 (m, 8 H), 4.74 (t, J = 7.8 Hz, 1 H), 6.24 (s, 1 H), 7.18-7.36 (m, 9 H), 7.74 (d, J = 7.5Hz, 2 H). 13C NMR (Me4Si, CDCl3): δ = 13.9, 15.3, 15.4, 16.0, 16.1, 21.5, 21.8, 23.3, 23.6, 25.7, 32.0, 95.7, 98.2, 120.7, 125.4, 125.5, 126.6, 127.3, 127.8, 128.3, 128.7, 130.9, 136.9, 137.8, 140.1, 140.5, 142.2, 146.9, 146.9, 158.7. HRMS (MALDI/DHB): m/z calcd for C34H41O [M + H]+: 465.3157; found: 465.3152.
Phenyl(2,3,4,5-tetraethylphenyl)methanone (5a): column chromatography on silica gel (PE-CH2Cl2, 1: 1), product as a yellow liquid. 1H NMR (Me4Si, CDCl3): δ = 1.10 (t, J = 7.5 Hz, 3 H), 1.18 (t, J = 7.5 Hz, 3 H), 1.20 (t, J = 7.5 Hz, 3 H), 1.21 (t, J = 7.5 Hz, 3 H), 2.59-2.78 (m, 8 H), 6.91 (s, 1 H), 7.41-7.46 (m, 2 H), 7.53-7.58 (m, 1 H), 7.82-7.85 (m, 2 H). 13C NMR (Me4Si, CDCl3): δ = 15.3, 15.4, 15.9, 16.5, 21.6, 22.0, 22.8, 25.5, 126.1, 128.2, 130.2, 130.3, 132.9, 137.1, 138.1, 138.1, 138.9, 140.8, 142.1, 199.8. HRMS (MALDI/DHB): m/z calcd for C21H27O [M + H]+: 295.2062; found: 295.2056.